TWI241581B - Optical recording medium - Google Patents

Abstract

An optical recording medium provided on a substrate with a recording layer, said recording layer comprising at least one kind of the trimethine-cyanine dye and an additive, wherein said the additive of recording layer selectively comprises the dye selected from the group consisting of the chemical compounds represented by the following general formula [10], [11], [12], and [13], ""EDG"" represents any electron-withdrawing substituted group such as alkylamino or anino group.

Description

1241581 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to an optical recording medium (optica 丨 recording medium), and particularly to a recording layer of an optical recording medium including the Based asymmetric trimethine-cyanine dye and an additive (addit 丨 νβ) can increase DVD-R's wnting sensjtivity. [Prior art] The use of laser light technology to store data on optical recording media is well known to the public. In the structure of a CD-R recording medium, the most important recording layer (rec0 "djng layer) is an organic dye layer, plus a reflective layer and a protective layer, which are sequentially layered on a transparent substrate to form a layer. Optical discs. When recording data on a disc, the laser is burned at a certain writing power by using laser light with a wavelength of 780 nm to 830 nm, causing the dye on the recording layer to decompose or deform, resulting in a burning area. The difference between the reflectivity and the unrecorded area. @This, the data stored on the disc can be read by using laser light with appropriate power, and the disc can also show the recording area and non-recording on the recording layer The reflectance difference in the region. ★ It is known that the shorter the wavelength of the laser light, the smaller the range of its light spot. Therefore, many researches are dedicated to Mao Zhan 爿 b to burn with laser light with a wavelength between 62nm to 690 nm. The discs are selected to increase the recording density ("ecordingdensity". "Recordable; Digital Versatile Audio-Visual Discs" (DVD-R)), a storage bin with a high recording density. The beloved discs are bound to become the mainstream of the new generation of recording media. At the same time, when performing data storage and retrieval, the wavelength range of laser light used by DVD_R is not equal to the wavelength range of laser light used by CD R. Therefore, it cannot be applied to __ recording layer materials. Therefore, according to the 1241581 specificity of dvd_r itself, it is necessary to find a suitable recording layer material. At present, the recording layer material of DVD-R, her heart dying, dye is one of the commonly used materials. U.S. Patent Nos. 5 976 658 and 6'291,045 both propose the use of trimethine-based cyanine dyes having a symmetrical or asymmetric jndo | enine structure in [^ 口 七. However, when the laser wavelength of a DVD-R recorder is changed from 635nm to 65nm (or higher), the material of the dye must be selected carefully. Because when the wavelength of the laser light becomes longer, the dye absorbance of the thin-film state at a wavelength of 650 nm also increases slightly. In other words, dyes originally suitable for burning at a wavelength of 635nm are not necessarily applicable when the burning wavelength becomes 650 nm, because the recording sensitivity at a specific wavelength and a recording layer with a lower light absorption rate require higher burning Power to write information 'Insufficient or too high programming sensitivity may cause programming failure. [Summary of the Invention] The US patent case number 6338888 proposes that at the writing wavelength of laser light, increasing the absorption rate of the organic layer dye can increase the recording sensitivity. Accordingly, the present invention proposes a new composition, which contains special additives, which can increase the programming sensitivity. The first object of the present invention is to propose an asymmetric indolenine cyanine dye having an electron-withdrawing group (EWG), which contains an indolenine ring or a benzoindolenine ring, as shown in the chemical formula [1] in FIG. 1 , [2], [3], [4]. 1241581 Figure 1

[2] [3] [4] The second object of the present invention is to provide an optical recording medium, the recording layer of which includes at least one asymmetric trimethine-cyanine dye with an electron-drawing group (EWG) and an additive The additive is an asymmetric trimethine-cyanine dye with an electron-donating substituted group (EDG). A second object of the present invention is to propose a synthetic reaction process to prepare an asymmetric trimethine-cyanine dye having an electron-drawing group (EWG), and an asymmetric tn_methine-cyanine dye having an electron-donating group (EDG). 1241581 The fourth object of the present invention is to provide an optical recording medium having better programming and reading characteristics when the laser light has a wavelength of 650 nm (or a longer wavelength). According to the present invention, the asymmetric trimethine-cyanine dye with an electron-drawing group (EWG) applied to the recording layer may be any one of the chemical formulas [1], [2], [3], [4], as shown in FIG. 1 As shown. "EWG" represents any electron-withdrawing group, such as cyano and nitro (ηK "0".%), And "r2" is selected from substituted or unsubstituted alkyl, benzene, respectively. (Phenyl), benzyl, alkylphenyl, and phenoxyalkyl ("R3", and "r4") are each selected from the group consisting of a hydrogen atom, a halogen atom, and an alkoxy group ( a 丨 koxy), hydroxide (hydroxy) or alkyl. Y is selected from a hydrogen atom, a halogen atom or a thiol group, and "X" is an anion 'system selected from F, CI, ΒΓ, I ·, ClO4-, BF4 ·, PF6' SbF6, 〇Ts , OMs, SCN, alkanoate (3 丨 | ^ 丨 51 ^ 〇 | 1310) and alkanoate (alkylcarboxylate). The dye solution of the present invention has a maximum absorptivity at a wavelength of 575 nm to 600 nm. Therefore, when the laser wavelength of a DVD-R recorder is 620 nm to 690 nm, the dye film has a proper absorptivity in this wavelength range. Used as a DVD-R recording layer material. The recording layer material of the present invention may optionally include a trimethine-cyanine dye as shown in the chemical formula.

A and "B" may be the same or different compounds of any one of the formulae [6], [7], [8], 1241581 [9]. (D) p [6]

-α

"D" is selected from the group consisting of substituted or unsubstituted alkyl, carboxyl, alkoxycarbonyl, alkylcarboxyl, and alkoxy (3 丨 1 <0; 1), Burning Hydroxy (3 丨 1 &lt; 117 € 1 ″ 0 乂 7), 3 ″ 311 ^ 丨, Alkenyl, Alkylamino, Alkylamino, Alkylamino, alkylsufonamide group, alkylcarbamoyl group, alkylsulfamoy group, hydroxyl group, hydroxyl atom, hydrogen atom, alkylalkoxyl, alkylhalide group, Completed alkylsulfonyl, or a hospital linked to metal ions or alkyl, phenyl, benzyl, alkylphenyl, and phenoxyalkyl Or thiol. P represents the number of substituents and is an integer greater than or equal to 1. "R5" and "R6" are selected from substituted or unsubstituted alkyl and phenyl groups, respectively. ), Benzyl (benzy 丨), alkylphenyl (a | ky | pheny 丨) 12 1241581 or phenoxyalkyl. "Z "Is a hydrogen atom, a halogen atom or an alkyl group, and X · is an anion 'is selected from the group consisting of F_, 〇Γ, ΒΓ, L, CIO /, BF%, PF6' SbF6, OTs-, OMs ·, SCNT, Alkyl sulfonate (a | ky | su 丨 fonate) and alkyl phosphonate (3 丨 1 ^ 丨 03 to 0 乂 7 丨 316). In the present invention, as the dye layer, The additive may be any one of the formulas [10], [11], [12], and [13].

[1〇]

[11] [12]

[13]

"EDG" stands for any electron-donating group such as amino, alkylamino, and methoxy. "R7" and "R8" are respectively selected from substituted or unsubstituted alkyl, phenyi, benzyl, a Ikylphenyl, and phenoxyalkyl ( p hen oxy alkyl). "R9" and "ho" are selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group 13 1241581 (aIkoxy), a hydroxy group, or an alkyl group, respectively. "Ya" is a hydrogen atom, a halogen atom or an alkyl group, and "X-" is an anion selected from the group consisting of F_, CI ·, ΒΓ, 1_, Cl04_, BF4 ·, PF6-, SbF6 ·, 〇 Ts-, OMs-, SCN ·, a Iky Isulfonate and alky I carboxyl ate group. The dye solution of the present invention has a maximum absorption rate at a wavelength of 575 nm to 620 nm. When the laser wavelength of a DVD_R recorder is 620 nm to 690 nm, it can be used as a recording layer material of a DVD-R. The dye layer of the present invention includes not only trimethine-cyanine dye having an electron-drawing group (EWG), but also trimethine-cyanine dye having an electron-donating group (EDG), which can improve the burning sensitivity and reduce DVD-R. Programming power required when writing data. The method for preparing the dye solution of the present invention is as follows: (1) A cyanine dye represented by the chemical formula [1], [2], [3] or [4] is dissolved in an organic solution such as a fluorinated alcohol (f Orinated alcohol), diacetone alcohol, diethylone ketone, methanol, toluene, toluene, cyclohexanone, acetylacetone, and dioxetane Dioxane. The concentration of this dye solution is 0.5% to 20% by weight. (2) Mix the cyanine dye represented by the formula [1], [2], [3] or [4] with the dye of the formula [5] whose weight percentage is less than 100%, and then dissolve it in an organic solution. The organic solution is, for example, fluorinated alcohol, diacetone alcohol, isoacetone, methanol, toluene, cyclohexanone, acetone, and dioxane. The concentration of this dye solution is 0.5% to 20% by weight. (3) The cyanine dye represented by the chemical formula [1], [2], [3] or [4] and the dye of the chemical formula [10], [11], [12] or [13] with a weight percentage of less than 50% Mix and dissolve in an organic solution. The organic solution is, for example, fluorinated alcohol, diacetone alcohol, isoacetone, methanol, toluene, cyclohexanone, acetone acetone, and dioxane. The concentration of the dye solution of 124 1241581 β is from 0.5% to 20% by weight. (4) Mix the dye of the chemical formula [5] with the chemical formula [10], [11], [12] or [13] of less than 50% by weight, and then dissolve it in an organic solution. The organic solution is, for example, alcohol, dipropanol, isopropyl alcohol, methanol, toluene, cyclohexanone, acetone, and dioxane. The concentration of this dye solution is 0.5% to 20% by weight. (5) The chemical formula [1] '[2]' [3] or [4] does not have a cyginjne dye with a chemical formula of less than 100% by weight [5] The dyes are mixed and then mixed with dyes of the formula [10], [11], [12] or [13] in a weight percentage of less than 50%, and then dissolved in an organic solution. The organic solution is, for example, fluorinated alcohol, diacetone alcohol, isopropyl ketone, methanol, toluene, cyclohexyl, acetamidine, and dioxane. The concentration of this dye solution is 0.5% to 20% by weight. According to the present invention, a method for manufacturing an optical recording medium includes the following steps: (1) First, a substrate is provided, and a material thereof can be selected from glass, epoxy resin, and methyl acrylate resin. ), Polycarbonate (polycarbonate), polyester resin (polyester resin), polyvinyl chloride resin (polyvinyl chloride resin), polyolefin resin (polyolefin resin). The substrate may have tracking grooves (grooves) or pits. (2) A dye solution is applied on a substrate by a spin coating method to form a dye film recording layer. (3) In addition to the recording layer, the optical recording medium also includes a reflection layer. This reflective layer has a high reflection coefficient, and can be vapor-deposited or single or multi-layer metal such as gold, silver, copper, copper, alloy, etc. (4) A protective layer can be applied after the reflective layer. The protective layer is formed to protect or enhance the characteristics of the optical recording medium. The method for forming the protective layer 15 1241581 can be coated on the metal reflective layer by coating an ultraviolet curing resin ("ad 丨 ation cu" e type "). Then it is hardened by ultraviolet light irradiation, that is, the optical recording medium of the present invention can be a single-sided = layered (smgle-s 丨 ded recording medium), with one substrate having a single-sided recording layer and another without grooves. The blank substrates are laminated to form an optical disc. The single-sided recording medium is formed by the steps (1) to (5). (6) The optical recording medium of the present invention may also be a double-sided recording medium (double- sided recording medium), which is formed by laminating two substrates with a single-sided recording layer. A single-sided optical recording medium is formed as shown in steps (1) to (5). The above-mentioned objects, features, and advantages of the present invention can be more clearly understood, and a preferred embodiment is given below in conjunction with the accompanying diagrams to describe in detail several embodiments and comparative examples as follows. [Embodiment] One side has The opposite of the EWG group Trimethine-cyanine dyes can be synthesized in different ways, such as the journal ^ 1995, India, 24, and U.S. Patent No. 6,306,478. Synthetic methods have been proposed for this. For example, the compound represented by chemical formula [1] (hereinafter referred to as the compound [1]) '' 'EWG' is Shi Xiaoji 'and “R3” and “Υ” are hydrogen radicals. The improved method of the present invention is shown in FIG. 2 *, when the reaction is carried out under normal pressure, ^ gets high yield # Compound [1]. 16 1241581

Circle 2

Nitration

Ri X_ [16]

In the chemical reaction shown in FIG. 2, high-yield compounds [15] and [16] can be obtained by the well-known calcination reaction (a | ky | atjon) and nitration reaction, respectively. Compound [16] is then dissolved in an alcohol solvent and reacted with n, N-diphenylformamidine under reflux. After that, a compound [17] with good quality and yield was obtained. Finally, the compounds [17] and [18] are treated with an appropriate solvent and stirred at room temperature, and then the compound [1] can be obtained in a high yield. Table 1 lists compounds [3] and [4] that can be synthesized by the method shown in FIG. 2. 17 1241581 Table 1

Compound No EWG Ri r2 r3 XY 1-1 CN ch3 ch3 H CI04 H 1-2 CN c2h5 ch3 H CI04 H 1-3 CN C3H7 ch3 H CI04 H 1-4 CN C4H9 ch3 H CI04 H 1-5 CN c8h17 ch3 H CI04 H 1-6 CN ch3 ch3 H PF6 H 1-7 CN C2H5 ch3 H PF6 H 1-8 CN C3H7 ch3 H PF6 H 1-9 CN C4H9 ch3 H PF6 H 1-10 CN c8h17 ch3 H SbF6 H 1-11 CN ch3 ch3 H SbF6 H 1-12 CN c2h5 ch3 H SbF6 H 1-13 CN C3H7 ch3 H SbF6 H 1-14 CN C4H9 ch3 H SbF6 H 1-15 CN CeHi7 C4H9 H SbF6 Me 1-16 CN C8Hi7 C4H9 H SbF6 Et 1-17 No. 2 ch3 ch3 H CI04 H 1-18 No. 2 c2h5 c2h5 H CI04 H 1-19 N〇2 C3H7 C4H9 H CI04 H 1-20 N〇2 C4H9 ch3 H CI04 H 1-21 N〇 2 C3H7 C4H9 H pf6 H 1-22 N〇2 c3h7 C4H9 H SbF6 H 1-23 N〇2 C3H7 C4H9 H bf4 H 1-24 N〇2 C3H7 C4H9 H CH3SO3 H

The recording layer material of the present invention may optionally further include a trimethine-cyanine dye as shown in Chemical Formula [5]. 18 1241581

"A" and "B" may be any one of the compounds represented by the chemical formulas [6], [7], [8], [9]. (D) p

€ C

[6]

(D) p

[7] [8] [9]

"A" and "B" may be the same or different compounds. "D" is any substituted or unsubstituted alkyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl group, alkoxyl group, hydrogen peroxide (Alklhydroxy) group, aralky group, alkenyl group, alkylamide group, alkylamino group, alkylsufonamide group, alkylcarbamoyl group, alkylsulfamoy group, hydroxide 19 1241581 (hydroxy) group, halogen atom, hydrogen atom, alkylalkoxyl, alkylhalide group, sulfur (3 丨 1 ^ 丨 5 mountain 1: 0 ″ 1) group, Or a carboxyl group linked to a metal ion or a thiol (311 ^ 丨) group, a benzene (16 ^ 7 gate 7 丨) group, a benzyl group, an alkylphenyl group, and a phenoxyalkyl group Or "thio". "P" represents the number of substituents and is an integer greater than or equal to 1. "R5" and "R6" may be the same or different and are respectively selected from substituted or non-substituted sulfur ( alkyl), phenyl, benzyl, alkylphenyl, or phenoxy (Phenoxyalkyl) group. "Z" is a hydrogen atom, a halogen atom or an alkyl group, and "X-" is an anion selected from the group consisting of F, CI, ΒΓ, Γ, ClO4, BF4 'PF6' SbF6_, 〇Ts_, 〇Ms ·, SCN_, a group consisting of a Iky Is ulfo nate and a Iky I carboxyl ate. In addition, the recording layer of the present invention can also be Includes at least one 1 ^ 6 ± 1 ^ 116-〇7311 to 6 dye with an electron-donating group (£ 06), as shown in chemical formulas [10], [11], [12], [13]. The trimethine-cyanine dye of the electronic group (EWG) also includes a dye layer having the trimethine-cyanine dye of the electron donating group (EDG), which can improve the programming sensitivity and reduce the required data when writing data to DVD-R. Programming power. 20 1241581

β, for example, "EDG" is an amino group, and "R3" and "γ" in formula ⑴ are as shown in formula [1〇]. As shown in the chemical reaction shown in Figure 3, the reduction of the nitro component in the chemical formula [1] with the reduction of π SnC ^ h ^ O'Fe / HCI ', and the "R, Compound. Note that "R7" Π 8 "in Chemical Formula [10] and" IV "and" R2 "in Chemical Formula [1] have the same positions in Figure 3. Figure 3

21 1241581 Compound [10] synthesized by a similar method, as shown in Table 2 Table 2 h2n

[10] ι r2 X-

Compound No Ri r2 X 10-1 Me Me CI〇4 10-2 Me Bu CI〇4 10-3 Pr Bu CI〇4 10-4 Bu Bu CI〇4 10-5 Me Me bf4 10-6 Me Bu bf4 10 -7 Pr Bu bf4 10-8 Bu Bu bf4 10-9 Me Me pf6 10-10 Me Bu PFe 10-11 Pr Bu pf6 10-12 Bu Bu PFe 10-13 Me Me SbF6 10-14 Me Bu SbF6 10-15 Pr Bu SbF6 10-16 Bu Bu SbF6 In another example, "EDG" in chemical formula [10] is an alkylamino group, and "R3" and "Y" (in chemical formula [1]) are hydrogen base. As shown in FIG. 4, by alkylating an ammonia component in the chemical formula [10] with an alkyl halide, a compound of the chemical formula [10 '] can be obtained. 22 1241581 Figure 4

[1〇]

[10.] The compound [10Ί] synthesized in a similar manner is shown in Table 3. Table 3 π Ri2-NV ^ r— r ^ n V [10 ·] I R1 x- I r2 Compound No Ri r2 Rl1 r12 X 10'-1 Me Me Me H CI〇4 10. · 2 Me Bu Bu H CI 〇4 10'-3 Pr Bu Pr H CI〇4 10.4 Bu Bu Pr Pr CI〇4 10.-5 Me Me Me Me bf4 10 · 6 Me Bu Bu Bu bf4 10.-7 Pr Bu Bu Bu bf4 10 * -8 Bu Bu Bu Bu bf4 10'-9 Me Me Me Me PF6 10.-10 Me Bu Bu Bu pf6 10.-11 Pr Bu Pr Pr PFe 10'-12 Bu Bu Pr Pr pf6 10'_13 Me Me Me Me SbF6 10'-14 Me Bu Bu Bu SbF6 10.-15 Pr Bu Pr Pr SbF6 10'-16 Bu Bu Pr Pr SbF6 23 1241581 DVD-R toiletry first provides a polycarbonate substrate, this substrate has The track pitch is 0 · 74 μηι, and only wobble signal (may also include pre-pit) is applied to it. One method of preparing the dye solution of the present invention is as follows: (1) Dissolving a cyanine dye represented by the chemical formula [1], [2], [3] or [4] in an organic solution; (2) ) Mix the cyanine dye represented by the chemical formula [1], [2], [3] or [4] with the dye of the chemical formula [5] whose percentage of reductive amount is less than 100%, and then dissolve in an organic solution; (3 ) Mixing the cyanine dye represented by the chemical formula [1], [2], [3] or [4] with the dye of the chemical formula [10], [11], [12] or [13] with a weight percentage of less than 50%, Then dissolve it in an organic solution; (4) Mix the dye containing the formula [5] with the formula [10], [11], [12] or [13] in less than 50% by weight, and then dissolve it in an organic solution Medium; and (5) Mix the cyanine dye represented by the chemical formula [1], [2], [3] or [4] with the dye of the chemical formula [5] whose weight percentage is less than 100%, and then with the weight percentage ® less than 50 % Of the dyes of the formula [10], [11], [12] or [13] are mixed and then dissolved in an organic solution. The organic solution is, for example, fluorinated alcohol, diacetone alcohol, methylethyl ketone, methanol, toluene, cyclohexanone, acetone acetone (306丨 7 丨 306 to 116) and dioxin (€ 11 (^ 3 gate 6). And the concentration of this dye solution is 0.5% to 20% by weight. In addition, the dye solution described above may also contain some monomers Oxygen inhibitors 24 1241581 (singlet oxygen quencher) and other compounds, such as metal complex, light absorbent, radical scavenger, etc. Then, the dye solution is rotated at a speed Spin-coated at 3000 rpm on the substrate. Then, it was dried at 70 ° C for 20 minutes to form a recording layer. The recording layer is a photosensitive dye layer with a thickness of about 1000 nm The material of the substrate can be selected from glass, epoxy resin, methacrylate resin, polycarbonate, polycarbonate resin, polyester resin, and polymer gas. Dilute (polyvinyl chloride resin), polyolefin resin (polyolefin resin). The base material can be grooves (grooves) or pits (pits). Thereafter, a reflective layer is deposited on the recording layer by sputtering. This reflective layer is a metal film with a southern reflection coefficient, such as gold, silver, silver, copper, metal, alloy, etc. The reflective layer can be formed on the recording layer by vapor deposition or sputtering. Moreover, the reflective layer can It is single or multiple layers. A protection layer can also be formed above the reflective layer. This protection layer contains an ultraviolet-curing resin, which is formed to protect or enhance the characteristics of optical recording media. The formation method is to cover a given reference surface (here, the surface of the substrate on which the recording layer and the reflection layer have been formed) with a solution containing a radiation curing type resin, and then lightly shoot The cover layer is cured. Then, 'two discs made as described above are overlapped and overlapped with a one-year adhesive layer' to obtain a double-sided recording medium ^ (required) It is to be noted that the optical recording medium of the present invention may be a single-sided recording medium (25 1241581 3 Η) with a single-sided recording layer, 1.85 (s, 6 Η), 4.15 (t, J = 7.4 Hz, 2 Η), 6.30 (d, J = 12 · 1 Hz, 1 H), 7_40 (t, J = 7_2 Hz, 1 Η), 7.53-7_66 (m, 4 H ), 7.79 (d, J = 8.85 Hz, 1 H) ^ 8.40 (dd, J = 12.1, 2.3 Hz, 1 H), 8.68 (d, J = 2.3 Hz, 1 H), 8.88 (d, J = 12.1 Hz, 1 H). Next, 12 g of the compound of the formula [17-1], 9 g of l-butyl ^^^-trimethylbenzoie) indoleninium chlorate? ^ 20 mL of Pyridine were mixed at room temperature and stirred for 3 hours. The solution was then poured into a 10% sulfuric acid solution. After filtration and crystallization from methanol, a compound of the formula [1-19] (15 g) can be obtained. Using a hydrogen nuclear magnetic resonance frequency spectrometer, the results can be obtained: λ · (TFP) = 577 nm; 1H NMR (300 MHz, CDCI3) 50.99 (t, J = 7.2 Hz, 3 H) ^ 1.06 (t, J = 7.2 Hz, 3 H) ^ 1.53-1.61 (m, 4 H) ^ 1.78 (s, 6 H) ^ 1.92 (quin., J = 7.2 Hz, 3 H), 2.03 (s, 6 H), 4.10 (t, J = 7.2 Hz, 3 H), 4.42 (t, J = 7.2 Hz, 3 H), 6.89 (d, J = 13.5 Hz, 1 H), 7.07 (d, J = 8.8 Hz, 1 H), 7.13 (d, J = 13.5 Hz, 1 Η) '7 · 47 (d, J = 8.8 Hz, 1 H), 7.54 (t, J = 7.6 Hz, 1 H) ^ 7.66 (t, J = 7.6 Hz, 1 H ) ^ 7.97-8.02 (m, 1 H), 8.13 (d, J = 8.6 Hz, 1 H), 8.16 (d, J = 2.1 Hz, 1 H), 8.29 (dd, J = 8.6, 2.1 Hz , 1 H), 8.51 (t, J = 13.5 Hz, 1 H). Next, 5-7 g of the compound of the formula [1.19] and 10.5 g of tin chloride dihydrate were dissolved in 40 mL of ethanol, and the mixture was heated and refluxed for 6 hours. After cooling to room temperature, it was poured into a 10% sodium hydroxide solution. After filtration and crystallization from methanol, a compound of the formula [10_3] (4_5 g) can be obtained. Measured with a hydrogen shuttle magnetic resonance frequency spectrometer, the results can be obtained: Amax (TFP) = 576 nm; 1H NMR (300 MHz, CDCI3) 50.95-1.02 (m, 6 Η), 1.46-1.58 (m, 4 Η), 1.73 (s, 6 H), 1_76-1_90 (m, 4 H), 2_01 (s, 6 Η), 4 · 07 (t, J = 7.4 Hz, 2 1241581 Η), 4 · 15 (t, J = 7_4 Hz, 2 Η), 6.38-6_47 (m, 2 Η), 6.69 (dd, J = 2.2, 8.4 Hz, 1 Η), 6.90-6.93 (m, 2 Η), 7.28-7.34 (m, 1 Η) '7.40-7.47 (m, 1 H) ^ 7.61 (t, J = 11 Hz, 1 H) ^ 7.94 (d, J = 8.9

Hz, 2 H), 8.10 (d, J = 8.9 Hz, 1 Η), 8.42 (t, 13.5 Hz, 1 H). Then, 5-7 g of the compound of the formula [10-3] and 3-3 g of n-Propyllodide were dissolved in 20 mL of ethyl acetate (Ethyl Acetate), and then the mixture was heated and refluxed for 24 hours. After cooling to room temperature, it was poured into a 10% concentration sodium hydrogenated solution. After filtration and crystallization from methanol, the compound of formula [10 -3] (4.0 g) can be obtained. Measured with a hydrogen nuclear magnetic resonance frequency spectrometer. The results are obtained. Amax (TFP) = 580 nm; 1H NMR (300 MHz,

The present invention will be described below in more detail with some examples of measurement and subtraction.

Each experiment will be explained in detail under CD Test / Experiment 3. 1241581 Table 4

Example UV Spectrum (nm) (TFP) Write (650 nm) Reflectance% Push-Pull% I14 / I14H Jitter% 1 577 OK 66.4 0.29 0.45 8.2 2 577 OK 55.3 0.60 0.60 5.7 3 577 OK 47.5 0.43 0.61 6.5 Comparative 1 566 Not available Comparative 2 568 Not available Experiment 1 First, a transparent substrate is provided. The substrate is a disc and the material is polycarbonate resin. Spiral grooves are formed on the disc. The gauge is 0. 74 μηι. The outer diameter of the substrate is about 120. mm, thickness is about 0.6 mm. Next, 5.0 g of the compound [1-19] was dissolved in 100 mL of TFP (2, 2, 3, 3-tetrafluoro-1-propanol), and the mixture was stirred at room temperature for 5 hours. The resulting solution was filtered through a polytetrafluoroethylene membrane (PTFE) with a pore size of 0.2 μm to prepare a dye solution. Then, the dye solution was spin-coated on the substrate at a rotation speed of 3000 rpm, and dried at 70 ° C for 20 minutes to form a photosensitive dye layer (recording layer) with a thickness of about 100 nm. . Thereafter, silver is sputtered on the recording layer to form a reflective layer having a thickness of about 100 nm. Among them, Argon is used as the sputtering gas. The sputtering power is 1.5 kW and the sputtering pressure is 1.0 × 1CT2 Torr. Next, an ultraviolet curing resin (No_575, Nippon Chemicals, lnc_) was coated and formed on the reflective layer. The other substrate made in the same manner as above was placed on the surface of the radiation-curable resin of the other substrate. When the resin is evenly dispersed between the two substrates, the same optical parameters as those in Experiment 1 are measured. The measurement results are shown in Table 4.

The experimental results show that the optical recording medium of control experiment 1 cannot be burned on a dvd_r machine with a wavelength of 650 nm. Comparative Experiment 2 The optical recording medium of Comparative Experiment 2 was manufactured as in Experiment 1, except that the dye compound [1 · 19] was replaced with the compound [20]. The recording layer of the optical recording medium was also measured with the same optical parameters as in Experiment 1. The measurement results are shown in Table 4.

The experimental results show that the optical recording medium of control experiment 2 cannot be burned on a dvd_r machine with a wavelength of 650 nm. It can be known from the above that when burning with a burner with a wavelength of 65, a recording disc containing only an asymmetric structure and a trimethine-Cyanine dye (_trimethine-Cyanine dye in the recording layer (Experiment bu 3)) is used. Discs containing trimethine-cyanine dyes with a symmetrical structure in the recording layer (control experiment), or package 31 1241581 trimethine-cyanine dyes with asymmetric structure but no electron-drawing group (control experiment 2) are more suitable. Optical disc test 2 Seven experiments were performed in optical disc test 2, which are experiments 4, 5, 6, 7, and control experiments 3, 4, and 5. The experimental results are summarized in Table 5. The following is a detailed description of each experiment Instructions.

Table 5

Example Write (650 nm) Reflectance% Push-Pull% I14 / I14H Jitter% 4 OK 57.6 0.34 0.6 7.4 5 OK 56.3 0.34 0.6 6.7 6 OK 64.9 0.30 0.58 7.5 7 OK 48.6 0.45 0.62 7.1 Comparative 3 Not available Comparative 4 Not available Comparative 5 Not available

Experiment 4 First, a transparent substrate was provided. The substrate is a disc and the material is polycarbonate resin. Spiral grooves are formed on the disc. The holding distance is 0_74 μητι °. The outer diameter of the substrate is about 120 mm. The thickness is approximately 0.6 mm. Next, 3.0 g of compound [1-21] and 0.6 g of compound [21] (derived from 32 1241581 compound [5]) were dissolved in 50 mL of TFP (2,2,3,3-tetrafluoro-1-propanol ) And stirred at room temperature for 5 hours. The resulting solution was filtered through a polytetrafluoroethylene membrane (PTFE) with a pore size of 0_2 μm to prepare a dye solution.

Then, the dye solution was spin-coated on the substrate at a speed of 3000 rpm, and dried at 70 ° C for 20 minutes to form a photosensitive dye layer (recording layer) with a thickness of about 100 nm. . Thereafter, silver is sputtered on the recording layer to form a reflective layer having a thickness of about 100 nm. Among them, argon (Argon) is selected as the spattering gas. The ore sputtering power is 1-5 kW, and the sputtering pressure is 1.0 × 1 (Γ2 Torr.) Next, a radiation-curing resin (No. 575, Nippon Chemicals, lnc_) is coated on the reflection Layer. Another substrate made in the same way as above is placed on the surface of the radiation-cured resin of the other substrate. When the resin is evenly dispersed between the two substrates, it is cured by radiation. Radiation curing resin. In this way, a double-sided optical disc with a thickness of 25 μηπ and a diameter of 32 mm to 120 mm can be obtained. Finally, a DVD-R burner is used. / RWA03, PIONEER burns the information on the disc, and uses the DVDT-R2, DVD-R / RW TESTER, DVDT-R2650 machine (for genera, EXPERT MAGNETICS Co., Ltd.) to perform reflectance. The track push-pull value is 33 1241581, and the measurement results are shown in Table 5.

The experimental results show that the optical recording medium of Comparative Experiment 3 cannot be recorded on a DVD-R machine at a wavelength of 650nm, but when the wavelength is set to 635nm, it can be successfully recorded. Comparative Experiment 4 The optical recording medium of Comparative Experiment 4 was manufactured as in Experiment 4, except that the dye was replaced with 2_0 g of compound [23] and 0.2 g of compound [21] (derived from compound [5]). The recording layer of the optical recording medium was also measured with the same optical parameters as in Experiment 4. The measurement results are shown in Table 5.

The experimental results show that the optical recording medium of Comparative Experiment 4 cannot be recorded on a dvD-R machine with a wavelength of 650 nm, but when the wavelength is set to 635 nm, it can be successfully recorded. 35 I241581 The measurement results are shown in Table 6. The optical recording medium of Experiment 9 was produced by the method of Experiment 4, except that the dye was 0-3 g of compound [1-22], 0.7 g of compound [21] (derived from compound [5]), and 0- 05 g of compound [ 10′-16] (derived from compound [10]). The same optical parameters as in Experiment 4 were also measured on the recording layer of the optical recording medium. The measurement results are shown in Table 6. The optical recording medium of Experiment 10 was produced by the method of Experiment 4, except that the dye was replaced with 0-9 g of the compound [1_22] and 0_06 g of the compound [10, · 16] (derived from the compound [10]). The recording layer of the optical recording medium was also measured with the same optical parameters as in Experiment 4. The measurement results are shown in Table 6. Comparative Experiment 6 The optical recording medium of Comparative Experiment 6 was produced as described in Experiment 4, except that the dye was replaced with 0.9 g of compound [10, -16] (derived from compound [1 10]). The optical layer of the optical recording medium was also measured with the same optical parameters as in Experiment 4. The measurement results are shown in Table 6. According to the above results, the presence of the compound [10] can reduce the burning power, but the content cannot exceed 50% of the dye composition. If the dye layer contains only the compound [1〇] ', the sensitivity of the optical disc will be too high to be able to Maintaining a high reflectivity, thus making the programming fail. In summary, although the present invention has been disclosed as above with a preferred embodiment, its combination is not intended to limit the present invention. Anyone skilled in this art will not depart from this. Within the spirit and scope of the invention, 'It can be modified and retouched. Therefore, the scope of protection of the present invention shall be determined by the scope of the attached patent application. [Brief Description of the Drawings] Figure 1 shows the electronic base. Asymmetric indolenine cyanine dye of EWG; Figure 2 is the chemical reaction of compound []] in an embodiment of the invention; Figure 3 is the chemical reaction of compound [1〇] in an embodiment of the invention; Fig. 4 is a chemical reaction of compound [1 (),] in an embodiment of the present invention; Table 1 lists the compounds synthesized by the method shown in Fig. 2 ", [2], [3], and [4] ; Table 2 lists the synthesis methods shown in Figure 3. Compound [1〇]; Table 3 lists the compounds [1〇,] synthesized by the method shown in Figure 4; Table 4 shows the experimental results of 5 experiments in the optical disc test 1; Table 5 shows the optical disc test 2 The experimental results of 7 of the experiments; and Table 6 shows the experimental results of the 5 experiments of the optical disc test 3. 39

Claims (1)

1241581 The scope of patent application: 1. An optical recording medium is formed on a substrate and has a recording layer. The recording layer includes up to y |, a trimethine_cyanine dye, and an additive. Additive, wherein the additive is selected from the group consisting of compounds [10], [彳 彳], [12], and [13]: 卬 gawar sr 111 Where "" EDG "represents an electron-donating group (e | ectron_donatjng substituted group);" R7 "and" R8 "are respectively selected from a substituted or unsubstituted alkyl group and phenyl group Group, benzyl group, benzene group (3 丨 1 &lt; 1 ^ 117 丨) group and phenoxy group (乂 73111 ^ 1) group of "卩 | 16"; "89" and "| ^ 1〇, Is selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxy group, a hyc | roxy 1241581 group, or an alkyl group; "Ya" is a hydrogen atom, a halogen atom, or an alkyl group; "X-" is An anion selected from the group consisting of F_, cr, ΒΓ, Γ, ci04_, BF4-, PF6 'SbF6 ·, 〇Ts-, 〇Ms, SCN, akykysulfonate, and alkynyl Group of alkylcarboxylates. 2_ The optical recording medium according to item 1 of the scope of the patent application, wherein the weight percentage of the [1〇], [11], [12], and [13] compounds in the dye composition is less than 50% 〇3 The optical recording medium according to item 1 of the scope of patent application, wherein "EDG" is an amino group. 4. The optical recording medium according to item 1 of the scope of patent application, wherein "EDG" is an alkylamino group. 5_ The optical recording medium according to item 1 of the scope of patent application, wherein "EDG" is a methoxy group. 6. The optical recording medium according to item 1 of the scope of patent application, wherein the trimethine-cyanine dye is selectively selected from the group consisting of compounds [1], [2], [3], and [4]: 1241581 [4] Among them, "EWG" represents an electron-withdrawing group; "RT and" R2 "are respectively selected from a substituted or unsubstituted alkyl group, a phenyl group, Benzyl group, alkylphenyl group and phenoxyalkyl group; "R3" and "R4" are selected from the group consisting of hydrogen atom, halogen atom, alkoxy group (aIkoxy) group, and hydrogen ( hydroxy) group or alkyl group; "Y" is selected from ® from hydrogen atom, halogen atom or alkyl group; and "X_" is an anion selected from F_, Cl_, Br_, |-, Cl04-, BF4 -, PF6_, SbF6_, 〇Ts_, 〇Ms ·, SCN ·, a group consisting of alkyl sulfonate and a Iky I carboxyl ate. 7. If the scope of patent application The optical recording medium according to item 6, wherein "EWG" is a nitro group. 42 1241581 8. The optical recording medium according to item 6 of the patent application scope, wherein "EWG" is a cyano group ( cyano group) 9. The optical recording medium according to item 1 of the scope of patent application, wherein the recording layer selectively includes a compound [5] Dye: Wherein, "A" and "B" are any one of compounds [6], [7], [8], [9]: [6] [7] [8] [9] "D" is any substituted or unsubstituted alkyl group, carboxyl group, alkoxycarbonyl group, alkylcarboxyl group, alkoxyl group, hydrogen peroxide (Alklhydroxy) group, aralkyl group, alkenyl group, alkylamide group, alkylamino group, alkylsufonamide group, alkylcarbamoyl group, alkylsulfamoyl group, hydroxyl group Group, halogen atom, hydrogen atom, hydrogen atom, alkylalkoxyl 43 1241581 (alkylalkoxyl), alkylhalide group, sulfur (3 丨 | ^ 丨 51 ^ 〇 ~ 丨) group, or metal Ionic or alkyl, phenyl, benzyl, alkylphenyl and phenoxyalkyl linked alkoxy or thio; "p" stands for substitution The number of groups is an integer greater than or equal to 1; "r5" and R6 "are respectively selected from a substituted or unsubstituted alkyl (a | kyl) group, a phenyl group, a benzyl group, Alkylphenyl or phenoxyalkyl; "Z" is hydrogen Atom, halogen atom or alkyl group; and "X_" is an anion selected from the group consisting of F, Cl ·, Br_, Γ, CIO, BF4, PF6 'SbF6, OTs, OMs_, SCN-, and calcined yellow In the group consisting of alkylsulfonate and alkylcarboxylate. 〇— An optical recording medium is formed on a substrate and has a recording layer. The recording layer includes: at least one trimethine-cyanine dye with an electron pulling group (EWG). The material is selectively selected from the group consisting of compounds [1], [2], [3] and [4]; and 44 1241581 At least one trimethine-cyanine dye having an electron-donating group (EDG) is selectively selected from the group consisting of compounds [10], [11], [12], and [13], 45 1241581 Wherein "" Rr, "R2", "R /" and "Rs" are respectively selected from substituted or unsubstituted alkyl groups, pheny 丨 groups, benzyl groups, and alkylbenzenes. (alkylphenyl) group and phenoxya | ky 丨 group; "Rs", "R4", "R9" and R10 are selected from hydrogen atom, halogen atom, and oxygen (a | k〇Xy ) Group, hydroxy group and alkyl group; "γ" is a hydrogen atom, a halogen atom or an alkyl group; "χ_" is an anion selected from the group consisting of f-, cr, Γ, Γ, CIO /, bf4_, pf6-, SbFe, OTs, OMs, SCN, burned lutein (a | ky | su | f〇nate) and burned complete salt (3 丨 1 ^ 丨 03 「130 乂 7 丨 316） Group of people. 46